JP6059765B2 - Stabilization of sunscreen in cosmetic compositions - Google Patents

Description

The present invention relates to a cosmetic composition containing an organic sunscreen that is stabilized so as not to decompose by including a 4-substituted resorcinol derivative in the composition.

Certain organic substances, known as sunscreens and whose molecules absorb harmful ultraviolet light, are widely used in cosmetic compositions to protect human skin from the damaging effects of sunlight. Yes. Sunscreens are disclosed in Nicoll et al. US Pat. No. 5,188,831 and D
It has been described in a number of publications, such as Obrowski et al. US Pat. No. 5,961,961. As is well known to those skilled in the art, the effectiveness of sunscreens is determined by the UV protection index (Su).
n Protection Factor, SPF).

An ideal sunscreen must be sufficiently stable both chemically and physically so that a qualified packaging life can be maintained during storage. It is particularly desirable for the product to maintain its protective effect for a long time after application of the product. That is, when the active substance is present in the skin, the active substance should be resistant to chemical or photodegradation, difficult to be absorbed from the skin, and difficult to be removed by perspiration, skin oil or water.

Sunscreens can be categorized in descending order of effectiveness: highly chromogenic monomeric organic compounds, inorganic compounds, and minimally chromogenic polymer organic solids.

U.S. Pat. Nos. 5,219,558 (Woodin, Jr. et al.) And 4,919,93.
No. 4 (Deckner et al.) Discloses a photoprotective composition comprising, as an active ingredient, a sunscreen agent classified as a color-forming monomeric organic compound. These examples specifically describe commercially available sunscreens such as octyl methoxycinnamate (Parsol MCX), benzophenone-3 (oxybenzone) and octyl dimethyl PABA.

Several problems are likely to occur in the chromogenic monomer organic compound. When organic sunscreens are included in a body care composition or attached to the skin, their sunscreen is lost. Also, many factors can cause their characteristics to change over time.

Among the many reasons why degradation occurs, one factor that causes a decrease in sunscreen factor (SPF) or changes in properties is that organic sunscreens are unstable to oxidation or photooxidation. Instability is an undesirable characteristic of organic sunscreens. Therefore, there is a need for substances that stabilize organic sunscreens against degradation. In particular, there is a need for substances that prevent oxidation or photooxidation of organic sunscreens.

US Pat. No. 5,188,831 US Pat. No. 5,961,961 US Pat. No. 5,219,558 U.S. Pat. No. 4,919,934

Applicants have now discovered that organic sunscreens are provided with oxidative or photooxidative stability when the body care composition includes a 4-substituted resorcinol derivative in combination with the organic sunscreen. Therefore, the present invention
a. From about 0.01% to about 20% by weight of an organic sunscreen;
b. About 0.0001% to about 50% by weight of general formula (I):

［式中、
Ｒ_１及びＲ_２の各々は独立に、水素原子、−ＣＯ−Ｒ、−ＣＯＯ−Ｒ、ＣＯＮＨＲを表し
、ここにＲは飽和または不飽和の線状、分枝状または環状のＣ_１−Ｃ_１８炭化水素基を表
し、
Ｒ_３は、（１）１−１８個の炭素原子、好ましくは２−１２個の炭素原子を有しており、
直鎖状アルキル基の１つまたは複数の水素原子がメチル基もしくはエチル基で置換されて
いるかまたは未置換のアルキル基を表す；例えば、Ｒ_３が直鎖状または分枝状のアルキル
を構成するか、あるいは、（２）一般式（ＩＩ）：

[Where:
Each of R ₁ and R ₂ independently represents a hydrogen atom, —CO—R, —COO—R, CONHR, wherein R is a saturated or unsaturated linear, branched or cyclic C ₁ -C ₁₈ represents a hydrocarbon group,
R ₃ has (1) 1-18 carbon atoms, preferably 2-12 carbon atoms,
One or more hydrogen atoms of a linear alkyl group is substituted by a methyl group or an ethyl group or represents an unsubstituted alkyl group; for example, R ₃ constitutes a linear or branched alkyl Or (2) general formula (II):

の基を表し、ここにＸは、水素；ＯＲ^１｛Ｒ^１は水素、（Ｃ_１−Ｃ_６）アルキルまたはア
リール−（Ｃ_１−Ｃ_６）アルキル｝；ＯＣＯＲ^２｛Ｒ^２は（Ｃ_１−Ｃ_６）アルキル、アリ
ール−（Ｃ_１−Ｃ_６）アルキルまたはフェニル｝；ハロゲン；（Ｃ_１−Ｃ_６）アルキル；
アリール−（Ｃ_１−Ｃ_６）アルキルまたはアリール−（Ｃ_１−Ｃ_６）アルキル；またはＮ
ＨＲ^１｛Ｒ^１は上記の定義と同義｝を表し、
ｎは一般式ＩＩの構造が５、６、７または８員環となるような０−３の数であり、
点線は場合によっては存在する二重結合を表す］
の４−置換レゾルシノール誘導体と、
ｃ．化粧品に許容されるビヒクルと、
を含む化粧組成物を提供する。

Wherein X is hydrogen; OR ¹ {R ¹ is hydrogen, (C ₁ -C ₆ ) alkyl or aryl- (C ₁ -C ₆ ) alkyl}; OCOR ² {R ² is (C ₁ -C ₆₎ alkyl, aryl - _(C 1 -C ₆₎ alkyl or phenyl}; _{halogen; (C} 1 -C ₆₎ alkyl;
Aryl- (C ₁ -C ₆ ) alkyl or aryl- (C ₁ -C ₆ ) alkyl; or N
HR ¹ {R ¹ is synonymous with the above definition}
n is a number from 0-3 such that the structure of general formula II is a 5, 6, 7 or 8 membered ring;
Dotted lines represent double bonds that may exist]
A 4-substituted resorcinol derivative of
c. A vehicle acceptable for cosmetics,
A cosmetic composition is provided.

The compositions of the present invention are aesthetically pleasing, have improved oxidative or photo-oxidative stability, prolonged sustained effects after application to the skin, and improved degradation during storage.

As used herein, the term “cosmetic composition” refers to compositions that are applied topically to human skin, such as leave-on and wash-off products.

The term “skin” as used herein includes the skin of the face, neck, chest, back, arms, armpits, hands, legs and scalp.

The term “inhibit” as used with respect to the oxidation of the sunscreen is meant to reduce the oxidation of the sunscreen by at least some amount, and at best to completely prevent it.

Except in the examples or unless otherwise clearly indicated, all numerical values herein that indicate the amount of material or reaction conditions, physical properties and / or use of the material are the term "about" It should be understood that All amounts are by weight unless otherwise specified.

For the avoidance of doubt, the term “comprising” means including, but not necessarily consisting of or consisting of. In other words, it is not necessary to exhaust the steps or options.

The present invention relates to a cosmetic composition that uses a 4-substituted resorcinol derivative to inhibit the degradation of organic sunscreens present therein. Preferably, 4 in the cosmetic composition of the invention.
-Substituted resorcinol derivatives have been used to stabilize organic sunscreens against oxidation or photooxidation. Depending on the type of cosmetic composition, other skin benefit substances and / or cosmetic additives may optionally be present. 4-Substituted resorcinol derivatives can also serve to provide a beneficial skin effect in addition to stabilizing the sunscreen.

The cosmetic composition of the present invention comprises an organic sunscreen that protects against the harmful effects of excessive sun bathing. Organic sunscreens suitable for the composition of the present invention are organic sunscreens having at least one chromophoric group that absorbs ultraviolet radiation in the range of 290-400 nm. Chromogenic organic sunscreen agents can be classified into the following types (specific examples in parentheses): p-aminobenzoic acid, salts thereof and derivatives thereof (ethyl, isobutyl, glyceryl esters; p-dimethylaminobenzoic acid).
Anthranilate (o-aminobenzoate; methyl, menthyl, phenyl, benzyl, phenylethyl, linalyl, terpinyl and cyclohexenyl esters); salicylate (octyl, amyl, phenyl, benzyl, menthyl, glyceryl and dipropylene glycol esters); ); Cinnamic acid derivatives (menthyl and benzyl esters, alpha-phenylcinnamonitrile; butylcinnamoyl pyruvate); dihydroxycinnamic acid derivatives (umbelliferone, methylumbelliferone, methylaceto-umbelliferone); Hydroxycinnamic acid derivatives (escretin, methyl esculetin, daphnetin and glycosides, esculin and daphnin); hydrocarbons (diphenylbutadiene, stilbene); dibenzalacetone Fine benzalacetophenone; naphthol sulfonate (2
Naphthol-3,6-disulfonic acid and sodium salt of 2-naphthol-6,8-disulfonic acid); dihydroxy-naphthoic acid and its salts; o- and p-hydroxybiphenyl disulfonate; coumarin derivatives (7-hydroxy, 7-methyl, 3-phenyl); diazole (2-acetyl-3-bromoindazole, phenylbenzoxazole, methylnaphthoxazole, various arylbenzothiazoles); quinine salt (bisulphate,
Sulfate, chloride, oleate and tannate); quinoline derivatives (8-hydroxyquinoline salt, 2-phenylquinoline); hydroxy- or methoxy-substituted benzophenones; uric acid and violuric acid; tannic acid and its derivatives (eg, hexaethyl ether); (Butyl carbyl) (6-propylpiperonyl) ether; hydroquinone; benzophenone (oxybenzone, thrisobenzone, dioxybenzone, benzoresorcinol, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy- 4
, 4'-dimethoxybenzophenone, octabenzone; 4-isopropyldibenzoylmethane; butylmethoxydibenzoylmethane; ethacrylene; and 4-isopropyl-dibenzoylmethane).

Particularly useful are: 2-ethylhexyl p-methoxycinnamate, 4,4'-t-butylmethoxybenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octyldimethyl p-aminobenzoic acid, digalloyl trioleate, 2 , 2-Dihydroxy-4
-Methoxybenzophenone, ethyl 4- [bis (hydroxypropyl)] aminobenzoate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl salicylate, glyceryl p-aminobenzoate, 3,3,5 -Trimethylcyclohexyl salicylate, methyl anthranilate, p-dimethylaminobenzoic acid or aminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, 2-phenylbenzimidazole-5-sulfonic acid, 2- (p-dimethylaminophenyl) ) -5
Sulfoniobenzoxazoic acid and mixtures thereof.

  Specific examples of commercially available suitable organic sunscreen agents are shown in the table below.

The amount of organic sunscreen in the body care composition is generally in the range of about 0.01% to about 20%, preferably in the range of about 0.1% to about 10%.

Preferred organic sunscreens are Pulsol MCX and Pulsol 1789 in view of their effectiveness and commercial availability.

Suitable 4-substituted resorcinol derivatives are known compounds. For example, a saturated carboxylic acid and resorcinol are condensed in the presence of zinc chloride, and the resulting condensate is converted into zinc amalgam /
Reduction with hydrochloric acid (Lille. J. Bitter, LA. Peiner. V, Tr
. Nauch-Issled. Inst. slantsev 1969, no. 18,1
27) or a method of reacting resorcinol with the corresponding alkyl alcohol at a high temperature of 200 to 400 ° C. in the presence of an alumina catalyst (UK Patent 1,581,428).

The compositions of the present invention generally have from about 0.01% to about 20% organic sunscreen and about 0.0000.
From 01% to about 50% 4-substituted resorcinol. A particular advantage of the composition of the present invention is that organic sunscreens are stabilized against oxidation or photooxidation by 4-substituted resorcinols.

  The stability of the composition of the present invention is represented by the following formula (I):

のレゾルシノール誘導体を有効成分として含む抗酸化剤の使用によって得られる。

It is obtained by using an antioxidant containing the resorcinol derivative as an active ingredient.

In the formula, each of R ₁ and R ₂ independently represents a hydrogen atom, —CO—R group (acyl group), —COO
-R group and CONHR group are represented. Here, R represents a saturated or unsaturated linear, branched or cyclic C ₁ -C ₁₈ hydrocarbon. In a preferred embodiment, each or both of R ₁ and / or R ₂ represents hydrogen. In a more preferred embodiment, both R ₁ and R ₂ represent hydrogen.

R ₃ is
(1) preferably having 1-18 carbon atoms, preferably 2-12 carbon atoms, wherein one or more hydrogen atoms of the linear alkyl group are replaced by methyl or ethyl groups Or represents an unsubstituted alkyl group; for example, R ₃ constitutes a linear or branched alkyl,
Or
(2) General formula (II):

の基を表す。式中の、Ｘは、水素；ＯＲ^１｛Ｒ^１は、水素、（Ｃ_１−Ｃ_６）アルキルま
たはアリール−（Ｃ_１−Ｃ_６）アルキル｝；ＯＣＯＲ^２｛Ｒ^２は、（Ｃ_１−Ｃ_６）アルキ
ル、アリール−（Ｃ_１−Ｃ_６）アルキルまたはフェニル｝；ハロゲン；（Ｃ_１−Ｃ_６）ア
ルキル；アリール−（Ｃ_１−Ｃ_６）アルキルまたはアリール−（Ｃ_１−Ｃ_６）アルキル；
またはＮＨＲ^１｛Ｒ^１は上記の定義と同義｝を表し、
ｎは一般式ＩＩの構造が５、６、７または８員環となるような０−３の数であり、
点線は場合によっては存在する二重結合を表す。

Represents a group of In which X is hydrogen; OR ¹ {R ¹ is hydrogen, (C ₁ -C ₆ ) alkyl or aryl- (C ₁ -C ₆ ) alkyl}; OCOR ² {R ² is (C _1- C ₆ ) alkyl, aryl- (C ₁ -C ₆ ) alkyl or phenyl}; halogen; (C ₁ -C ₆ ) alkyl; aryl- (C ₁ -C ₆ ) alkyl or aryl- (C ₁ -C ₆ ) Alkyl;
Or NHR ¹ {R ¹ is as defined above}
n is a number from 0-3 such that the structure of general formula II is a 5, 6, 7 or 8 membered ring;
The dotted line represents a double bond present in some cases.

In the above formula (I), an unsubstituted linear alkyl group represented by R and preferably having 2-12 carbon atoms includes ethyl, propyl, butyl, pentyl, hexyl. Groups, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. In these linear alkyl groups, one or more hydrogen atoms may be substituted with a methyl group or an ethyl group. Specific examples of the substituted alkyl group are isopropyl group, isobutyl group, isoamyl group or 2-methylexyl group. Preferred alkyl groups are R
Is an alkyl group representing an ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl group. Most preferred alkylresorcinols are those in which R represents an ethyl, butyl or hexyl group.

Where R ₃ is represented by the general formula II in the above formula (I), such compounds are referred to herein as the general formula III

の４−シクロ−置換レゾルシノールと呼ぶ。
式中の
Ｘは、水素；ＯＲ^１｛Ｒ^１は水素、（Ｃ_１−Ｃ_６）アルキルまたはアリール−（Ｃ_１−Ｃ
_６）アルキル｝；ＯＣＯＲ^２｛Ｒ^２は（Ｃ_１−Ｃ_６）アルキル、アリール−（Ｃ_１−Ｃ_６
）アルキルまたはフェニル｝；ハロゲン；（Ｃ_１−Ｃ_６）アルキル；アリール−（Ｃ_１−
Ｃ_６）アルキルまたはアリール−（Ｃ_１−Ｃ_６）アルキル；またはＮＨＲ^１｛Ｒ^１は上記
の定義と同義｝を表し、
ｎは０−３の数であり、
点線は図示の位置に場合によっては存在する二重結合を表す。

Of 4-cyclo-substituted resorcinol.
X in the formula is hydrogen; OR ¹ {R ¹ is hydrogen, (C ₁ -C ₆ ) alkyl or aryl- (C ₁ -C
₆ ) alkyl}; OCOR ² {R ² is (C ₁ -C ₆ ) alkyl, aryl- (C ₁ -C ₆
) Alkyl or phenyl}; halogen; (C ₁ -C ₆ ) alkyl; aryl- (C _1-
C ₆ ) alkyl or aryl- (C ₁ -C ₆ ) alkyl; or NHR ¹ {R ¹ is as defined above}
n is a number from 0-3;
The dotted line represents a double bond that may be present at the position shown.

More specific examples of 4-cyclo-substituted resorcinol include, for example, the following compounds:
(A) a compound of formula (III) in which a single bond in the formula bonds two carbon atoms with a dotted line;
(B) a compound of formula (III) in which n represents 1;
(C) a compound of formula (III) in which X represents hydrogen;
(D) a compound of formula (III) in which X represents hydrogen, methyl or ethyl;
(E) a compound of formula (III) in which n represents 0;
(F) a compound of formula (III) in which n represents 2;
(G) A compound of formula (III) wherein X in the formula represents benzyloxy.

Preferred compounds of formula (III) are 4-cyclopentylresorcinol, 4-cyclohexylresorcinol, 4-cycloheptylresorcinol and 4-cyclooctylresorcinol. The most preferred compounds of formula (III) are 4-cyclohexylresorcinol and 4-cyclopentylresorcinol.

The amount of 4-substituted resorcinol effective to inhibit the oxidation of organic sunscreens can be determined experimentally. The organic sunscreen and the 4-substituted resorcinol derivative are about 1:
1000-1000: 1, preferably 1: 100-100: 1, more preferably 1: 1-
Present in a weight ratio of 1: 100.

The amount of resorcinol derivative is preferably in the range of about 0.00001% to about 10%, more preferably in the range of about 0.001% to 7%, most preferably 0.01% of the total amount of the cosmetic composition.
-In the range of about 5%.

Preferred cosmetic compositions are those suitable for application to human skin, and in some cases preferably contain skin benefit substances.

Suitable skin beneficial substances are anti-aging agents, wrinkle inhibitors, skin lightening agents, acne inhibitors and sebum inhibitors. Specific examples of these include alpha-hydroxy acids and esters, beta-hydroxy acids and esters, polyhydroxy acids and esters, kojic acids and esters,
Ferulic acid and ferrate derivatives, vanillic acid and esters, dionic acid (sebacic acid,
Azoline acids, etc.) and esters, retinol, retinal, retinyl ester, hydroquinone, t-butylhydroquinone, mulberry extract, licorice extract, and resorcinol derivatives other than the 4-substituted resorcinol derivatives mentioned above in this text (in this case ,
It serves both two functions: the function of providing oxidative stabilization of the organic sunscreen and the function of providing skin beneficial effects such as lightening).

Skin benefit substances are usually used in addition to cosmetic bases with the organic sunscreen compounds and resorcinol derivatives of the present invention. Suitable carriers acceptable for cosmetics are known to those skilled in the art.
The cosmetic base may be any base commonly used for skin benefit substances and therefore does not need to be strictly defined. Specific forms of cosmetic preparations that may be incorporated with the skin benefit agent of the present invention are creams, ointments, emulsions, lotions, oils, packs and non-woven wipes. Cream bases are, for example, beeswax, cetyl alcohol, stearic acid, glycerin, propylene glycol, propylene glycol monostearate, polyoxyethylene cetyl ether and the like. Lotion bases are, for example, oleyl alcohol, ethanol, propylene glycol, glycerin, lauryl ether, sorbitan monolaurate and the like.

A cosmetically acceptable vehicle can act as a diluent, dispersant or carrier for the skin benefit ingredient in the composition so as to facilitate its distribution when the composition is applied to the skin.

The vehicle may be aqueous, anhydrous or an emulsion. Preferably the composition is an aqueous or emulsion, in particular a water-in-oil or oil-in-water emulsion, preferentially an oil-in-water emulsion. If water is present, the water is 5% -99% by weight, preferably 20% -70%.
% By weight, optimally in the range 40% -70% by weight.

In addition to water, relatively volatile solvents can also be used as carriers within the compositions of the present invention. Monovalent C ₁ -C ₃ alkanols are most preferred. These include ethyl alcohol, methyl alcohol and isopropyl alcohol. The amount of monovalent alkanol is 1% by weight-70.
% By weight, preferably 10% -50% by weight, optimally in the range 15% -40% by weight.

Skin relief materials can also be used as cosmetically acceptable carriers. These will be in the form of silicone oils and synthetic esters. The amount of emollient will range from 0.1% to 50% by weight, preferably 1% to 20% by weight.

Silicone oils can be classified into volatile and non-volatile varieties. As used herein, the term “volatile” means a material having a vapor pressure that can be measured at ambient temperature. The volatile silicone oil is preferably selected from cyclic or linear polydimethylsiloxanes containing 3-9, preferably 4-5, silicon atoms. Linear volatile silicone materials generally have a viscosity of less than about 5 centistokes at 25 ° C., while cyclic materials typically have a viscosity of less than about 10 centistokes. Nonvolatile silicone oils useful as an emollient material include polyalkyl siloxanes, polyalkylaryl siloxanes, and polyether siloxane copolymers. Essentially non-volatile polyalkylsiloxanes useful in the present invention include, for example, polydimethylsiloxanes having a viscosity of from about 5 to about 25,000,000 centistokes at 25 ° C. A preferred non-volatile emollient useful in the compositions of the present invention is polydimethylsiloxane having a viscosity of about 10 to about 400 centistokes at 25 ° C.

Suitable ester emollients are listed below:
(1) Alkenyl or alkyl esters of fatty acids having 10-20 carbon atoms. Specific examples thereof include isoarachidyl neopentanoate, isononyl isonanonoate, oleyl myristate, oleyl stearate and oleyl oleate;
(2) ether-esters such as fatty acid esters of ethoxylated fatty alcohols;
(3) Polyhydric alcohol esters such as ethylene glycol mono- and di-fatty acid esters, diethylene glycol mono- and di-fatty acid esters, polyethylene glycol (
200-6000) mono- and di-fatty acid esters, propylene glycol mono- and di-fatty acid esters, polypropylene glycol 2000 monooleate, polypropylene glycol 2000 monostearate, ethoxylated propylene glycol monostearate, glyceryl mono- and di-fatty acid esters Polyglycerol poly-fatty ester, ethoxylated glyceryl monostearate, 1,3-butylene glycol monostearate, 1,3-butylene glycol distearate, polyoxyethylene polyol fatty acid ester, sorbitan fatty acid ester, and polyoxy Ethylene sorbitan fatty acid esters are fully useful polyhydric alcohol esters;
(4) Wax esters such as beeswax, spermaceti, myristyl myristate, stearyl stearate, arachidyl behenate; and (5) sterol esters typified by cholesterol fatty acid esters.

Fatty acids having 10-30 carbon atoms are also included in the cosmetically acceptable carrier for the composition of the present invention. Representative of this type are pelargonic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, linoleic acid, ricinoleic acid, arachidic acid, behenic acid and erucic acid.

A polyhydric alcohol type humectant may also be used as a cosmetically acceptable carrier in the composition of the present invention. Moisturizers help improve the effectiveness of skin soothing agents, reduce skin dryness and improve skin feel. Typical polyhydric alcohols are glycerol, polyalkylene glycols, more preferably alkylene polyols and their derivatives, such as propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene glycol and their derivatives, sorbitol, hydroxy There are propyl sorbitol, hexylene glycol, 1,3-butylene glycol, 1,2,6-hexanetriol, ethoxylated glycerol, propoxylated glycerol and mixtures thereof. The amount of humectant can be any value within the range of 0.5% -30% by weight of the composition, preferably 1% -15%.

In the composition of the present invention, a thickener may be used as part of a cosmetically acceptable carrier. Typical thickeners are cross-linked acrylates (eg, Carbopol 982), hydrophobically modified acrylates (eg, Carbopol 1382), cellulosic derivatives and natural gums. Useful cellulosic derivatives include sodium carboxymethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, ethylcellulose and hydroxymethylcellulose. Natural gums suitable for the present invention include guar gum, xanthan gum, sclerotium, carrageenan,
Pectin and a combination of these gums. What is the amount of thickener? It may range from 0.0001% to 5% by weight, usually 0.001% to 1% by weight, optimally 0.01% to 0.5% by weight.

A cosmetically acceptable carrier in a total amount of water, solvent, silicone, ester, fatty acid, humectant and / or thickener of 1% -99.9%, preferably 80% -99% by weight. Configure.

An oil or oily material may be present with the emulsifier to form a water-in-oil or oil-in-water emulsion that is highly dependent on the average hydrophilic-lipophilic balance (HLB) of the emulsifier used.

Surfactants may also be present in the cosmetic composition of the present invention. For leave-on products, the total surfactant concentration is 0.1% -40%, preferably 1-20% by weight of the composition.
Optimally, it will be in the range of 1% to 5% by weight. In the case of wash-off products such as cleansers and soaps, the overall surfactant concentration will range from about 1% to about 90%. The surfactant can be selected from anionic, nonionic, cationic and amphoteric surfactants.

Particularly preferred nonionic surfactants are 1 mole per hydrophobic group 2-100 moles of ethylene oxide or propylene oxide condensed with C ₁₀ -C ₂₀ ones with fatty alcohols or fatty acid hydrophobic group; 2-20 moles of alkylene oxide fused _C 2 _{-C 10} alkyl phenols and; ethylene glycol mono - and di - fatty acid esters; fatty acid monoglyceride; sorbitan, mono- - and di _-C 8 _{-C 20} fatty acid; block copolymers (ethylene oxide / propylene oxide); and polyoxy Ethylene sorbitan as well as combinations thereof. Alkyl polyglycosides and sugar fatty acids (eg methyl gluconamides)
Are also suitable nonionic surfactants.

Preferred anionic surfactants include soap, alkyl ether sulfates and sulfonates, alkyl sulfates and sulfonates, alkylbenzene sulfonates, alkyl and dialkyl sulfosuccinates, C ₈ -C ₂₀ acyl isethionates, acyl glutamates, C ₈ - C ₂₀ alkyl ether phosphates and combinations thereof.

The cosmetic composition of the present invention optionally contains a foaming surfactant. “Foaming surfactant”
The term “surfactant” means a surfactant that generates bubbles or bubbles when water is added and mechanically stirred. Preferably, the foaming surfactant should be non-irritating. This means that it provides a sufficient cleansing or cleansing effect but does not dry the skin excessively and must meet the above foaming standards. The cosmetic composition of the present invention may contain a foaming surfactant at a concentration of about 0.01% to about 50%.

The cosmetic compositions of the present invention include various other optional ingredients such as plasticizers, elastomers, calamines, pigments, antioxidants, chelating agents and perfumes, and additional sunscreens such as UV scattering agents. Can be added. Typical examples of UV scattering agents are refined titanium oxide and zinc oxide.

Other minor auxiliary ingredients may also be included in the cosmetic composition. These ingredients include colorants, opacifiers and fragrances. Such other minor auxiliary ingredients are 0.001% by weight-2 of the composition.
Any value within the range of 0% by weight is acceptable.

The intended use of the composition of the present invention is primarily a body care product that is applied externally to human skin to protect the exposed skin from the harmful effects of excessive sun exposure.

In use, a small amount of, for example, about 0.1 to about 5 ml of the composition is applied to the exposed area of the skin from a suitable container or applicator and then applied to the skin using hands, fingers or a suitable device if necessary. Spreading and / or rubbing.

The cosmetic composition of the present invention is a lotion having a viscosity of 4,000-10,000 mPas, a fluid cream having a viscosity of 10,000-20,000 mPas, or 20,000-100,000 mPas. Or it can be mix | blended as a cream which has the viscosity beyond it. All of these viscosities are those measured at 25 ° C. The composition can be packaged in a suitable container suitable for its viscosity and intended use by the consumer. For example, lotions or fluid creams can be packaged in bottles, roll ball applicators, propellant driven aerosol devices or containers equipped with suitable finger operated pumps. When the composition is a cream, it can be easily filled into a squeeze container such as a non-deformable bottle or tube or a vase with a lid.

Accordingly, the present invention also provides a closed container containing a cosmetically acceptable composition as defined herein.

The following specific examples further illustrate the invention, but the invention is not limited to these examples. In all examples, organic sunscreens were obtained from Givaudan Corp.

(Example 1-8)
A group of compositions within the scope of the present invention was prepared and shown in the table below. The composition is expressed in weight percent.

The composition of Example 1-7 in the previous table and the composition of Example 8 which was a base composition to which no resorcinol derivative was added were prepared by the following procedure. Heat Phase A to 75 ° C. Phase B is heated to 75 ° C. in a separate container from the Phase A container. Then stop heating and combine the two phases with stirring. Premix Phase C and warm, then add to Phase A and Phase B immediately after mixing. Phase D is predissolved and added to the main pot at 60 ° C. The mixture is cooled to 40 ° C. and then packaged.

Example 9
The light stability of organic sunscreens in various cosmetic compositions in the presence and absence of resorcinol derivatives was measured. For this purpose, Examples 5-8 in the previous table were tested. The resorcinol derivatives in these examples were tested at equivalent molar concentrations (18.09 mM) in the formulations. The monochromatic light protection index (Monochromatic Protecti
on Factor, MPF). The light stability of Pulsol 1789, a UVA organic sunscreen agent in these compositions, was evaluated by monitoring the decrease over time. A comparative composition (Example 8) was prepared by removing the resorcinol derivative from the composition of Examples 5-7.

Procedure for measuring MPF of cosmetic formulations MPF data were collected using an SPF-290 Analyzer with an integrating sphere manufactured by Optometrics USA. The software creates a monochromatic light protection index (MPF) for every 5 nm portion over the 290 nm-400 nm scan range. The MPF is calculated from the reciprocal of transmission at each of these wavelengths (λ or gamma) (MPF = 1 / T _λ ). Since SPF or UV protection index is a weighted average of MPF values at various wavelengths in the UV spectrum, MPF is an indicator of the UV protection properties of a dermatological composition. Accordingly, a decrease in MPF with time is an index representing a decrease in sunlight blocking activity.

The light source of the SPF-290 instrument is a 125 W xenon arc lamp operating at 75 W, and its beam passes through a wire attenuator and a Schott UG05 filter. The filter attenuates light rays above 500 nm of the light source and alters the spectral distribution to approximate the relative solar radiation spectrum in the UV-B and UV-A regions. The intensity of the beam incident on the sample is approximately 16 mW / cm ² , which corresponds to approximately eight times the UV intensity of the midday summer sun rays in the northeastern United States. The minimum time of UV beam irradiation of the test site required for each full scan is about 30 seconds.

In-line Fastie that collects the light beam after passing through the sample in an integrating sphere and is optimized for UV efficiency
-Split into discontinuous wavelength bands with an Ebert grating monochromator. The band collides with the detector and generates a signal proportional to the intensity of the light beam. The MPF value of 360 nm (VA) was used for the photostability evaluation of the sunscreen of Examples 5-8.

UV transparent quartz plate (10.16 cm × 10.48 cm × 0.32 cm, 4 ″ × 4
1/8 ″ × 1/8 ″) was first calibrated by placing it on a fully automatic programmable XY stage and scanned to correct the background. Next, the product thin film was uniformly applied with a spatula to the calibrated quartz plate. An 8-pass wet thin film applicator (Paul Gardner Company, Inc.) with a pass width of 7.62 cm (3 ″) was used.
. 5 mil gap (1 mil = 0.001 inch, ie about 25 micrometers)
Was used to slide the applicator by hand from end to end of the plate and allowed the film to dry for 15 minutes. A quartz plate provided with a product thin film is placed on an XY stage, and a baseline measurement value (t = 0)
Was scanned. The XY stage was set to scan six preset sites on the product film. While storing the product formulation in a 120 ml amber glass jar at 25 ° C., the same 6 pre-set sites were scanned every 15 minutes until 105 minutes to monitor the gradual decline in sunscreen performance.

Between each measurement, the product film was removed from the UV light source and placed in an ambient temperature drawer. The MPF values shown in the table represent the average of readings taken from six different sites at each time point.

上の表３の結果は、本発明の組成物にレゾシノール及びその誘導体を添加すると、追加
の安定性が得られたことを証明する。

The results in Table 3 above demonstrate that additional stability was obtained when resorcinol and its derivatives were added to the compositions of the present invention.

The data in the table above was found to be statistically significant with a p-value less than 0.0001. The p-value was determined as follows.

Objective- Compare the light blocking of the base composition of Example 8 to the composition of Examples 5-7 containing resorcinol derivatives. It is expected that the product containing the resorcinol additive will slow down the light blockage more slowly. The reciprocal of light transmission is used as a virtual measure of light blockage.

Method- Apply product to glass slides and measure 6 points on each slide. Three slides are used for each of the four products. As a result, a total of 18 points are measured for each product. The first measurement is taken after a 15-minute drying period in accordance with the sunscreen test standard. Measurements are then taken every 15 minutes until 120 minutes, for a total of 8 time points. Mixed action type taking into account the correlation between the measurement points in the slide and the measurement time points
effects) Perform an analysis of variance.

Analysis of variance examines time effects, product effects, and time-product interactions. A significant time-product interaction will indicate that there is some difference in the rate of change of light blockage between products. It can be judged from a contrast comparison whether the rate of change of the base of Example 8 is significantly different from the rate of change of the three products containing resorcinol. Each product regression model will fit a function to the data for each product. The function will evaluate the relationship between time and the inverse of light transmission. The function will evaluate linear time effects.

Results -p-value of 0.0 for all product effects, time effects, product-time interaction
Significant results are obtained that are less than 001. In contrast, the composition of Example 8 and Example 5-
7 shows that there is a significant difference of p = 0.0001 between the resorcinol derivative-containing composition of 7.

It should be understood that the specific forms of the invention illustrated and described herein are merely representative.
Changes may be made to the exemplary embodiments, such as suggested without limitation, without departing from the teachings that are apparent from the description. Accordingly, the full scope of the invention should be determined based on the claims.

Claims (3)

a. 0.01 wt% to 20 wt% organic sunscreen,
b. 0.0001% to 50% by weight of the general formula I:

[Where:
Each of R ₁ and R ₂ independently represents a hydrogen atom, —CO—R, —COO—R, —CONHR, wherein R is a saturated or unsaturated linear, branched or cyclic C ₁ — Represents a _C18 hydrocarbon group,
R ₃ represents an alkyl group having 1-18 carbon atoms or is represented by the general formula (II):

Wherein X is hydrogen; OR ¹ {R ¹ is hydrogen, (C ₁ -C ₆ ) alkyl or aryl- (C ₁ -C ₆ ) alkyl}; OCOR ² {R ² is ( C ₁ -C ₆ ) represents alkyl, aryl- (C ₁ -C ₆ ) alkyl or phenyl}; halogen; (C ₁ -C ₆ ) alkyl; aryl- (C ₁ -C ₆ ) alkyl; or NHR ¹ { R ¹ represents the same definition as above,
n is a number from 0-3 such that the structure of general formula II is a 5, 6, 7 or 8 membered ring;
Dotted lines represent double bonds that may exist]
A 4-substituted resorcinol derivative of
c. A cosmetically acceptable carrier;
Wherein the organic sunscreen agent is selected from the group consisting of octylmethoxycinnamate, butylmethoxydibenzoylmethane and mixtures thereof, and the 4-substituted resorcinol derivative is 4-ethylresorcinol, 4-propylresorcinol, 4 A cosmetic composition characterized in that it is selected from the group consisting of isopropylresorcinol, 4-butylresorcinol, 4-pentylresorcinol, 4-hexylresorcinol and mixtures thereof, provided that: Such a composition does not comprise 0 wt% N-acetylglucosamine, 0.3 wt% 4-butylresorcinol and 7.0 wt% octylmethoxycinnamate. Furthermore, alpha-hydroxy acids and esters, beta-hydroxy acids and esters, polyhydroxy acids and esters, kojic acids and esters, ferulic acids and ferrate derivatives, vanillic acids and esters, dionic acids and esters, retinol, retinal A skin benefit agent selected from the group consisting of resorcinol derivatives other than 4-resorcinol derivatives, mixtures thereof, and retinyl esters, hydroquinone, t-butylhydroquinone, mulberry extract, licorice extract, and a mixture thereof. Cosmetic composition. Skin benefit materials, alpha - hydroxy acids, beta hydroxy acids, polyhydroxy acids, hydroquinone, characterized in that it is selected from t- butylhydroquinone 及 beauty mixtures thereof Cosmetic composition according to claim 2.